Process for manufacturing ar-tetrahydronaphthylamine compounds



Patented July 25, 1933 0E WiEsDoEE, NEARoo LoGNE-oN-EiininiiiNE, EENS@ Kon-TEN, 0E EEANKEonT-ON- THEMAiN-EECHENi-imii, AND si-iEoLoEIeoosr, or LEVERKUSEN, VNEi-in COLOGNE- oN-:riiE-isi'iiNE,v GEEMENY, nssieNcE-s Ee i; e. EAEBEN-iNniisrEiE AKTIENGE- sELLscHeET, Ascaron-errori oEeEEifiANY Y PROCESS Eon. MANUEiic'iURiNG AR"'rErEAiiYniioNAELiTHYLAi/IINE ooMEoiiNDs' No Drawing. Original application iilcd October 2, 1926, Serial No. 139,226, andin Germany Octoberl, y

1925. Divided and this application filed December 2S, 19223. Serial. No. 328,620.

rlhis application is la division of" ourap- .plicatioii Serial No. 139,226,1iled V@c tober 2,19%,iioivPatentNo- 1,782,4'29.; The methods hitherto linown'iorpreparing hydrogenated and aromatic amiiiocompounds do not give satisfactoryfresults. The

liydrogenation of primary aromatic amines .as described -by Y Ipatieiv. (cf. ",Bciichtedefr 1 deutschen Chem. Gesellschaft,UNOS/page 991)-y With hydrogen and .catalysts.V under pressui'egoes on very; slowly and undesirable by-pi'oducts are formed. Sabatier .and Sen derens have. reduced secondary: and tertiary -amineslin the present 'of finely divided nickel (in which formula R means an arylresidue of the' benzene- -or of thenaphthalene,series, X1 means hydrogen, Which `may be replaced iby` alkyl, `arallylyaiid'aryl,"and..X2 means alkyl,Y Whichinay be v replaced by aralkyl ior acyl) add hydrogen quickly and smoothly When treatedfin a liquid. phase With hydrogen in the lpresence oi' .a hydrogenaton catalyst under pressure. Nickel, cobalt, copper O i mixtures of these metals or oxidesth'ere- "of, advantageously'precipitated Aon ,ar substratuni of large surface,`4 herein-after referred to simply by the -term base metal hydrogenatioiicatalysts may be used as the hydrogenation catalysts. alkyl, aralliylor aryl derivatives the de- `sired hydrogenated basesare obtained iinmediately,l While inthe case. of .acyl derivatives'the lacylgroiip may be removed b saponication, the free hydrogenated bases being thus formed.

`The productshobtained bythe method described above are partially nevvfand inayfbe fused iortlie prepara-tion of pharmaceutical and othervalu'able technical 'products.

Eln case of the.

EELIXXLINGEMANN 0E EiiANiEosfr,oN-mieiE-isiiiiN-MMNKUE, WIEHELM' LOMMEL,

f :Inorder to further illustrate'our inventionthe following examples are given, the parts beingby Weight andalltemperatures in centigrade` degrees, vbut it is understood that our invention is notlimited tothe par ticular products or reacting conditionsV nientionedtheiein.

' li'rrafln'plcl 50 parts of acetyl-dna-phthylainine Aare ih cated With 15`0parts of tetrahydi'onaphtha- "lelie and -l'paitfof a kieselguhr catalyst containing about .25%- nickel 'iii'A an autoclave While stirring Yunder hydrogen pressure of about 15430 atmospheres. Y The additionof lhydrogen.b egins at afteinperature of a*`lit-V 1 Y tle'a'bove 110O C., but it isjadvisableto raise the temperature to 1GO-1809 C( When tivoY molecules of hydrogen have been added, the,

mass While still hot is -iiltered oil from the hydro-a-naphthylamine ofthe formula:

form of line; needles of the. melting point 1590 C.- Tlieyield isfnearly quantitative.

.so separates out in Van alreadyv pure Vstate in "f l tetra'hydro-a-naphthylaniine is obtained in oim Vof anl oil, Wliichdoes not solidify at ordinary temperatures Yand which boils at 2759-0. under normal pressure.

Emmi 50 j'rpaits' puiefv acteyl-naphthylamine are heated in an autoclave While stirring v With 200 parts of dekahydronaphthalene in the presence of a catalyst containing nickel under a hydrogen pressure of aboutQO atlinospheies. 5 When 2 moleculesof l'hydrogen have been added thermass isy filtered. I The catalyst. From the liltrate acetyl-ar-tetral@ y steam. From the residue the acetyl-ar-tetrahydro--naphthylamine of the formula H2 EI NHoooH Hz- H l HzH can be extracted with ether.

of anoil Which solidiiies on cooling. The -acetyl compound may be saponied by treatment with hydrochloric acid.` The artetrahydro--naphthylamine thus obtained has the boilingpoint 271-273o C. at normal pressure (Bamberger, Ber. der deutsch.

chem. Gesellschaft 23, page 882, gives the boiling point as 275-2770- 0.).Y

Emample 3 35 parts of benZoyl--naplithylamine, 70V

parts ofv dekahydronaphthalene vand 1.7

lparts Vof. a kieselguhr catalyst containing 15% nickel are heated in an vautoclave While stirring under a hydrogen pressure of 15- 30 atmospheres to about 170 C. `Two molecules of hydrogen are -absorbed very quickly under these conditions.;v When this point is reached, the operationv is interrupted. The benzoyl-ar-tetrahydro--naphthylamine of the formula 1 4 NH-coous i Y a i thus obtained, which has the melting point 165-167 C. yields on saponiication the base already described in Example 2.

E ample ,4

If instead ofthe acetyl compound used 'in Example 1 formyl-a-naphthylamine is `reduced under similar` conditions, the product obtained yields .after's'aponification the same ar-tetrahydro-a-naphthylamine described in Example 1.

' In the Vsame way tetrahydro--naphthyl-' amine may be obtained naphthylamine. -Y

Also phthalic-a-naphthalide can be readily reduced according to the same process. The reduction product yields after saponi- Iication the same ar-tetrahydro-a-naphthylamine as describedin Example' Y1.

i yE'omnple 5 -V Y Y l20 parts of 2-acetyl amino-naphthalene-S- 'carboxylic ethylester, meltingat 123- C. are hydrogenated under a hydrogen pressure "of 15? 0 atmospheres While stirring inthe presence of 100 partsv of dekahydronaphthale'ne After the ether i isV distilled off the product remains in form Y and 0.4 parts of a kieselguhr catalyst containing about 15% nickel. Two molecules of hydrogen are quickly absorbed-at a temperature of 1200 C. By saponifying the hydrogenated ester under the usual conditions, the free 2-amino-3-ar-tetrahydronaphthoic acid of the probable formula:

Hz- NH:

m- -cooH 1305-180@ Cf rapidly and yieldafter Isaponica'tion bases, which are hydrogenate'd in the nucleus Which is not `substituted, by the amino group.

lVe claim:4 1. A 'process which comprises treating amino compounds vof the naphthalene series i of the general formula: y

.y 4' CX00 wherein- Y stands for hydrogen or COO- alkyl, in case Y is alkyl, the group "'N\X2 C105 Vstands in 2-position, and'Xl-stands for-hygroup, .X2 for anY'acyl-group,` in -a liquid phasewith hydrogen under superatmospher'ic i P1110 pressure 1in-the, presence `of a base 'metal hydrogenation catalyst and fsa'ponifying the ar-tetra-hydroacylamino compounds thus obtained. f Y Y' 2. A Vprocess which comprises treatingll amino compounds rof the naphthalenje .series of the `general formula: f

wherein Y Stands for -hydrogen01- l alkyl, i117 Case Y is COOalkyl, 'the 'group Y /X1v v stands in 2-position and X1 stands A"for rhy- -dro`genor'anfacyl-group and X2 or Aan acylgroup, in 'a liquid phase with :hydrogen 11n- 5130 pounds thus obtained.

der superatmospheric pressure in the presence of a base metal hydrogenaton catalystVV and saponfying the ar-tetrahydroacylf lamino compounds thus obtained.

tetrahydona formula 3. A process which comprises treating an 2-acylaminonaphthalene-B-carboxylic ester of the general formula:

@Nasen phthoic acid of the vprobable OOOH l ydroacylamino com- 4. As anew compound the 2-amino-3'ar- 75 crystallizingifrom'organic solvents in color- FELI less fine needles meltin at ISO-182 C. -KLINGEMANN ERNST KORTEN.

. WILHELM LOMMEL. THEODOR GOOST.

v'125 I f 

